Method for textile treatment for spandex containing fabrics

ABSTRACT

A method of treating textile which is yarn or fabric containing spandex fibres, comprising contracting the textile with a perfume so that the perfume is deposited on the fabric. The perfume contains a mixture of fragrance materials which preferentially deposit on the spandex fibres. The yarn of fabric may be made up into garments.

This invention relates to the treatment of textiles containing spandexfibres.

At the present time, many garments are made from fabric which contains amixture of fibres, a proportion of which are elastic, so that the fabrichas the ability to stretch and to recover from stretch. Spandex fibresare commonly used for this purpose. The term “Spandex” has been adoptedas a generic term by the United States Federal Trade Commission todenote a manufactured fibre in which the fibre-forming substance is along chain synthetic polymer composed of at least 85% of a segmentedpolyurethane. A discussion of such fibres can be found in “History ofSpandex Elastomeric Fibres” by A. J. Ultee, which is a chapter startingat page 278 in Man-Made Fibres: Their Origin and Development, edited byR. V. Seymour and R. S. Porter, Elsevier 1993. Spandex fibres are alsoreferred to as “elastane” or “elasthane” fibres.

Another discussion of such fibres is found under the heading “SegmentedPolyurethanes” at page 613 of Handbook of Textile Fibres by J. GordonCook, 5th Ed. Merrow Publishing Company 1984. Further description ofelastanes and their applications can be found in “Synthesefasern:Grundlagen, Technologie, Verarbeitung und Anwendung”, B von Falkei(editor), Verlag Chemie (1981). Commercially available elastanes arewell known, in particular as sold under the name LYCRA®, a registeredtrade mark of DuPont de Nemours and Company. Patents relating to suchfibres include U.S. Pat. No. 5,000,899, U.S. Pat. No. 5,288,779 and U.S.Pat. No. 5,362,432.

The deposition of perfume onto garments and other fabrics duringlaundering has been established for many years. Perfume is incorporatedinto laundry products such as detergent compositions for fabric washingand rinse conditioners for softening the fabrics.

Although the perfume serves to cover the base odour of such a productand to give the unused product an attractive fragrance, it also depositson the fabric.

Certain perfumes have the ability to provide deodorant action againstbody odour, either when directly applied to human skin, or when includedin a laundry product. Such perfumes are described in EP-B-3172, U.S.Pat. No. 4,304,679, U.S. Pat. No. 4,278,658, U.S. Pat. No. 4,134,838,U.S. Pat. No. 4,268,341 and U.S. Pat. No. 4,289,641, U.S. Pat. No.5,482,635 and U.S. Pat. No. 5,554,588.

SUMMARY OF THE INVENTION

We have now found that a number of fragrance materials used in perfumeryare able to deposit and then be retained better on spandex fibres thanon a number of other textile fibres.

Delivery of fragrance materials to fabric can take place during washing,as is well known. The present invention appreciates that the applicationof perfume to textiles containing spandex fibres can be utilised in thetreatment of textiles which are newly made—that is to say textile goodswhich have never been worn as garments by a consumer.

Therefore in one aspect the present invention provides a method oftreating textile which is yarn or fabric containing spandex fibres,comprising contacting the textile with a perfume so that the perfume isdeposited on the fabric. Preferably, the fabric is unworn. It may havebeen made up into a garment.

In a related second aspect, the invention provides textile which is yarnor fabric containing spandex fibres, having perfume deposited on thetextile. Preferably, the fabric is unworn. It may have been made up intoa garment.

We have observed that a range of fragrance materials deposited on suchtextiles will still be perceptible on the fabric, even after severalwashes of the fabric using laundry products with a different perfume, ornone.

The invention also provides use of a perfume composition in thetreatment of textile which is yarn or fabric containing spandex andother fibres, to deposit fragrance materials at a greater concentrationon the spandex fibres than on the other fibres. Preferably, the fabricis unworn.

In significant forms of this invention, the perfume used to treat thetextile (or the combination of fragrance materials deposited thereon) isa deodorant perfume. Then when the textile is made into a garment, thatgarment will have an in-built deodorant property.

DETAILED DESCRIPTION

The various aspects of this invention, preferred forms and materialsuseful therein will now be discussed in greater detail.

Textiles

The textiles to which this invention relates include spandex fibres. Asmentioned earlier, this term denotes a manufactured fibre in which thefibre forming substance is a long chain synthetic polymer compoundcomposed of at least 85% of a segmented polyurethane.

Thus the polymer which is spun into spandex fibres is a copolymerincorporating urethane linkages. Generally the polymer containsso-called soft (i.e. lower melting) segments which may be polyalkyleneethers or polyesters and so-called hard (i.e. higher melting) segmentswhich are portions derived from the reaction of an isocyanate and achain extender which is typically a diamine.

The soft segments may be poly(tetramethylene)ethers, possibly containingsubstituted tetramethylene glycol residues as described in U.S. Pat. No.5,000,899. Organic diisocyanates which may be used include conventionaldiisocyanates, such as diphenylmethane-4,4′-diisocyanate, also known asmethylene-bis(4-phenylisocyanate) or “MDI”, 2,4-tolylene diisocyanate,methylene-bis(4-cyclohexylisocyanate), isophorone diisocyanate,tetramethylene-p-xylylene diisocyanate, and the like. MDI is preferred.

Chain extenders used in producing the hard segment of the fibrespreferably include one or more of ethylenediamine (EDA),1,3-propylenediamine, 1,4-cyclohexanediamine, hydrogenatedm-phenylenediamine (HPMD), 2-methylpentamethylene diamine (MPMD) and1,2-propylene diamine. More preferably, the chain extender is one ormore of ethylenediamine, 1,3-propylenediamine, and1,4-cyclohexanediamine, optionally mixed with HPMD, MPMD and/or1,2-propylenediamine.

Spandex fibres with poly(tetramethylene) ethers as the soft segments aremarketed by DuPont de Nemours International S.A. under the registeredtrade mark LYCRA® of DuPont de Nemours and Company.

Spandex fibres are generally mixed with other fibres such as cotton,polyamide, wool, polyester and acrylics and made into yarn which is thenmade into fabric. The content of spandex fibres is usually in a rangefrom 0.5% by weight of the yarn or fabric up to 50%, more usually from 1to 30% by weight of the yarn or fabric.

A wide range of garments may contain spandex fibres in the fabric,including active sports wear, intimate apparel, hosiery and a variety ofready to wear casual clothing.

The textiles which are treated with a perfume composition prior towearing may be yarn which is later made into fabric, or may be fabric inthe form of a web or lengths from a web which have not yet been madeinto garments, or may possibly be garments.

Preferably the treatment with a perfume composition is carried out whiletreating with other material in a conventional process step, especiallya wet stage in which the yarn or fabric is treated with a finishingagent to improve its hand or appearance.

However, the perfume composition may be included directly into thespandex fibre. A fabric may be made using the spandex fibre alone.Alternatively, the spandex fibre may be covered or mixed with otherfibres and made into a yarn which is then made into fabric.

The materials which may be applied to fabric in a conventional finishingtreatment include resins to confer stiffness, fabric stability orpermanent press, fabric softeners, flame retardants, fabric brighteners,anti-snag agents, materials to confer soil or stain resistance and waterrepellants.

Techniques which are conventionally used to apply such materials arepadding and exhaustion, both well known in the technology of textilemanufacture.

Treatment with a perfume composition in accordance with this inventioncan be carried out by including the perfume composition in the liquorused in a process as above.

The amount of perfume deposited on the fabric in a treatment stepcarried out on fabric will generally be from 0.001% to 1% by weight ofthe fabric.

Fragrance Materials

We have found that a range of fragrance materials deposit well on, orare retained well on, spandex fibres. Such materials include thefollowing two categories:

Category A

hydroxylic materials which are alcohols, phenols or salicylates, with anoctanol/water partition coefficient (P) whose common logarithm (log₁₀P)is 2.5 or greater, and a gas chromatographic Kovats index (as determinedon polydimethylsiloxane as non-polar stationary phase) of at least 1050.

Category B

esters, ethers, nitriles, ketones or aldehydes, with an octanol/waterpartition coefficient (P) whose common logarithm (log₁₀P) is 2.5 orgreater, and a gas chromatographic Kovats index (as determined onpolydimethylsiloxane as non-polar stationary phase) of at least 1300.

The octanol-water partition coefficient (or its common-logarithm ‘logP’)is well known in the literature as an indicator of hydrophobicity andwater solubility (see Hansch and Leo, Chemical Reviews, 71, 526-616,(1971); Hansch, Quinlan and Lawrence, J.Organic Chemistry, 33, 347-350(1968). Where such values are not available in the literature they maybe measured directly, or estimated approximately using mathematicalalgorithms. Software providing such estimations are availablecommercially, for example ‘LogP’ from Advanced Chemistry Design Inc.

A requirement for log₁₀P of 2.5 or more calls for materials which aresomewhat hydrophobic.

Kovats indices are calculated from the retention time in a gaschromatographic measurement referenced to the retention time for alkanes[see Kovats, Helv.Chim.Acta 41, 1915 (1958)]. Indices based on the useof a non-polar stationary phase have been used in the perfumery industryfor some years as a descriptor relating to the molecular size andboiling point of ingredients. A review of Kovats indices in the perfumeindustry is given by T Shibamoto in “Capillary Gas Chromatography inEssential Oil Analysis”, P Sandra and C Bicchi (editors), Huethig(1987), pages 259-274. A common non-polar phase which is suitable is100% dimethyl polysiloxane, as supplied for example under a variety oftradenames such as RP-1 (Hewlett-Packard), CP Sil 5 CB (Chrompack), OV-1(Ohio Valley) and Rtx-1 (Restek).

Materials of low Kovats index tend to be volatile and are not retainedwell on many fibres.

We have found that when perfumery materials have partition coefficientas above and a relatively high value of Kovats index, deposition andretention on spandex tends to be greater than on other fibres.Preferably therefore, the perfume composition contains at least 50 wt %,better at least 70 or 80 wt % of materials from the categories above.

We have found that there is a particularly high enhancement ofdeposition and retention on spandex, compared to other fibres, withmaterials within the above categories and having a Kovats index of notmore than 1600. These sub-sets of categories A and B may be termedcategories A′ and B′. Preferably therefore, the perfume compositioncontains at least 10 wt %, better at least 20 wt % or 25 wt % of suchmaterials. In some preferred perfumes the amount of fragrance materialsfrom categories A′ and B′ is at least 40 wt % in total.

Such fragrance materials are of mid-range volatility (i.e. intermediatebetween the volatile perfume materials used as “top-notes” and thematerials of low volatility which are customarily used as “base notes”in perfumes). These materials of mid-range volatility are often notperceptible on other fabrics such as cotton, polyamide and polyesterafter washing and drying.

Category A includes alcohols of general formula ROH where the hydroxylgroup may be primary, secondary or tertiary, and the R group is an alkylor alkenyl group, optionally branched or substituted, cyclic or acyclic,such that ROH has partition coefficient and Kovats properties as definedabove. Alcohols of Kovats index 1050 to 1600 are typicallymonofunctional alkyl or arylalkyl alcohols with molecular weight fallingwithin the range 150 to 230.

Category A also includes phenols of general formula ArOH, where the Argroup denotes a benzene ring which may be substituted with one or morealkyl or alkenyl groups, or with an ester grouping —CO₂A, where A is ahydrocarbon radical, in which case the compound is a salicylate. ArOHhas partition coefficient and Kovats index as defined above. Typically,such phenols with Kovats index 1050 to 1600 are monohydroxylic phenolswith molecular weight falling within the range 150 to 210.

A sub-set of fragrance materials which are particularly preferred arethose with a partition coefficient of 1000 or more, i.e. log₁₀P of 3 ormore, and a Kovats parameter of 1100 up to 1600.

Some examples of hydroxylic ingredients which fulfil the above criteriafor category A′ are listed as a table below. Materials which are in theparticularly preferred sub-set are marked with an asterisk. Semitrivialnames are those used in standard texts known within the perfumeindustry, particularly: Common Fragrance and Flavor Materials by Bauer,Garbe and Surburg, VCH Publ., 2nd edition (1990), and Perfume andFlavour Materials, Steffen Arctander, published in two volumes by theauthor (1969).

Examples of fragrance materials in category A′1-(2′-tert-butylcyclohexyloxy)-butan-2-ol*3-methyl-5-(2′,2′,3′-trimethylcyclopent-3-enyl)- pentan-2-ol*4-methyl-3-decen-5-ol* amyl salicylate*2-ethyl-4(2′,2′,3-trimethylcyclopent-3′-enyl)but-2-enol*      (Bangalol,TM) borneol* carvacrol* citronellol* 9-decenol* dihydroeugenol*dihydrolinalol* dihydromyrcenol dihydroterpineol* eugenol geraniol*hydroxycitronellal* isoamyl salicylate* isobutyl salicylate* isoeugenol*linalol menthol* nerolidol* nerol* para tert-butyl cyclohexanol*phenoxanol* terpineol tetrahydrogeraniol* tetrahydrolinaloltetrahydromyrcenol thymol* 2-methoxy-4-methylphenol    (Ultravanil, TM)(4-isopropylcyclohexyl)-methanol*

Some examples of fragrance materials which are in category A but whichhave Kovats index above 1600 (so as to fall outside category A′) are:

benzyl salicylate

cyclohexyl salicylate

hexyl salicylate

patchouli alcohol

farnesol

Category B is eaters, ketones, aldehydes, nitriles or ethers which havean octanol-water partition coefficient whose common logarithm (log₁₀P)is at least 2.5, and a Kovats index of at least 1300 (non-polar phase).

Ingredients of Category B are of general formula RX, where X may be in aprimary, secondary or tertiary position, and is one of the followinggroups: —COA, —OA, —CO₂A, —CN or —CHO. The groups R and A arehydrocarbon residues, cyclic or non-cyclic and optionally substituted.In some forms of this invention, category B excludes any material with afree hydroxy group, so that where a hydroxyl group is present, thematerial should be considered only for Category A membership. Typically,the materials of Category B with Kovats index not exceeding 1600 (whichmay be called category B′) are monofunctional compounds with molecularweights in the range 160 to 230.

A sub-set of particularly preferred fragrance materials within categoryB′ is those with a Kovats parameter falling within the range 1350 up to1600, and possessing a molecular structure containing a ring, such asphenyl or cycloalkyl.

A number of fragrance materials which fulfil the above criteria forcategory B′ are listed in the table below. Materials which are in theparticularly preferred sub-set are marked with an asterisk.

Examples of fragrance materials in category B′1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1- carbaldehyde* 1-(5′,5′-dimethylcyclohexenyl)-pent-en-1-one* 2-heptyl cyclopentanone*2-methyl-3-(4′-tert-butylphenyl)propanal 2-methylundecanal 2-undecenal2,2-dimethyl-3-(4′-ethylphenyl)-propanal3-(4′-isopropylphenyl)-2-methylpropanal 4-methyl-4-phenylpent-2-ylacetate* allyl cyclohexyl propionate* allyl cyclohexyloxyacetate* amylbenzoate* methyl ethyl ketone trimers    (Azarbre, TM) benzophenone*3-(4′-tert-butylphenyl)-propanal    (Bourgeonal, TM) caryophyllenecis-jasmone* citral diethyl acetal citronellal diethyl acetalcitronellyl acetate phenylethyl butyl ether    (Cressanther, TM)damascone, alpha-* damascone, beta-* damascone, delta-* decalactone,gamma-* dihydro isojasmonate* dihydrojasmone* dihydroterpinyl acetatedimethyl anthranilate* diphenyl oxide* diphenylmethane dodecanaldodecen-2-al dodecane nitrile 1-ethoxy-1-phenoxyethane    (Efetaal, TM)3-(1′-ethoxyethoxy)-3,7-dimethylocta-1,6-diene      (Elintaal Forte (TM)4-(4′-methylpent-3′-enyl)-cyclohex-3-enal    (Empetaal, TM) ethyltricyclo[5.2.1.0-2,6-]decane-2-carboxylate*1-(7-isopropyl-5-methylbicyclo[2.2.2]oct-5-en-2-yl)-1- ethanone*   (Felvinone, TM) allyl tricyclodecenyl ether*    (Fleuroxene, TM)tricyclodecenyl propanoate*    (Florocyclene, TM) gamma-undecalactone*n-methyl-n-phenyl-2-methylbutanamide*    (Gardamide, TM) tricyclodecenylisobutyrate*    (Gardocyclene, TM) geranyl acetate hexyl benzoate*ionone alpha* ionone beta* isobutyl cinnamate* isobutyl quinoline*isoeugenyl acetate* 2,2,7,7-tetramethyltricycloudecan-5-one*     (Isolongifolanone, TM) tricyclodecenyl acetate*    (Jasmacyclene,TM) 2-hexylcyclopentanone    (Jasmatone, TM)4-acetoxy-3-pentyltetrahydropyran*    (Jasmopyrane TM) ethyl2-hexylacetoacetate    (Jessate, TM) 8-isopropyl-6-methylbicyclo[2.2.2]oct-5-ene-2- carbaldehyde    (Maceal, TM) methyl4-isopropyl-1-methylbicyclo[2.2.2]oct-5-ene-2- carboxylate* methylcinnamate aipha iso methyl ionone* methyl naphthyl ketone* nerolinnonalactone gamma nopyl acetate* para tert-butyl cyclohexyl acetate4-isopropyl-1-methyl-2-[1′-propenyl]-benzene*      (Pelargene , TM)phenoxyethyl isobutyrate* phenylethyl isoamyl ether* phenylethylisobutyrate* tricyclodecenyl pivalate*    (Pivacyclene, TM) phenylethylpivalate*    (Pivarose, TM) phenylacetaldehyde hexylene glycol acetal*2,4-dimethyl-4-phenyltetrahydrofuran    (Rhubafuran, TM) rose acetone*terpinyl acetate 4-isopropyl-1-methyl-2-[1′-propenyl]-benzene     (Verdoracine, TM) yara* (4-isopropylcyclohexadienyl)ethyl formate

Examples of fragrance materials which lie within category B, but haveKovats index above 1600 and so are outside category B, are listed in thefollowing table:

Within category B but outside category B′ amyl cinnamate amyl cinnamicaldehyde amyl cinnamic aldehyde dimethyl acetal cinnamyl cinnamate1,2,3,5,6,7,8,8a,-octathyro-1,2,8,8-tetramethyl-2-acetyl naphthalene     (iso E super (TM) cyclo-1,13-ethylenedioxytridecan-1,13-dione     (ethylene brassylate) cyclopentadecanolide    (Exaltolide, TM)hexyl cinnamic aldehyde1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]- 2-benzopyran   (Galaxolide, TM) geranyl phenyl acetate6-acetyl-1-isopropyl-2,3,3,5-tetramethylindane      (Traseolide, TM)1,1,2,4,4,7-hexamethyl-6-acetyl-1,2,3,4- tetrahydronaphthalene   (Tonalid, TM)

As indicated above, it is particularly preferred to utilise a perfumecomposition which has deodorant properties. Preferably, the perfume is adeodorant perfume giving a Malodour Reduction Value of at least 0.5,preferably at least 0.9, in the Malodour Reduction Value test describedbelow and which is an adaptation of the test described in EP-A-147191and corresponding U.S. Pat. No. 4,663,068.

The Malodour Reduction Value Test

In this test, the Malodour Reduction Value of a deodorant perfume ismeasured by assessing its effectiveness, when applied to fabric, inreducing body malodour when the fabric so treated is placed in contactwith the axillae (armpits) of a panel of human subjects, and held therefor a standard period of time. From subsequent olfactory evaluation bytrained assessors, a Malodour Reduction Value can be calculated sogiving a measure of the effectiveness as a deodorant of the perfumeunder test.

Stage 1 is preparation of the perfume treated fabric. A test fabric issubjected to a textile finishing which applies perfume to the fabric ata predetermined percentage of perfume composition, by weight of thecloth. A control fabric is given similar treatment, with or withoutperfume, depending on the purpose of the test. Depending on the purposeof the test, the fabrics may subsequently be washed and dried.

The test and control fabrics are cut into 20 cm×20 cm squares fortesting.

Stage 2 is the carrying out of the test. A team of three Caucasianfemale assessors of minimum age 20 years is selected to carry outolfactory evaluation on the basis that each is able to rank correctlythe odour levels of the series of standard aqueous solutions ofisovaleric acid listed below, and each is able to assign a numericalscore, corresponding to the odour intensity of one of these solutions,to the body malodour of a shirt insert after has been worn in theaxillary region by a male subject for a standard period of time.

A panel of 40 human subjects for use in the test is assembled fromCaucasian male subjects of age within the range of from 20 to 55 years.By screening, subjects are chosen who develop axillary body malodourthat is not unusually strong and who do not develop a stronger bodymalodour in one axilla compared with the other. Subjects who developunusually strong body malodour, for example due to a diet includingcurry or garlic, are not selected for the panel.

For two weeks before the start of the test, the panel subjects areassigned an unperfumed, non-deodorant soap bar for exclusive use whenwashing and are denied the use of any other type of deodorant orantiperspirant. At the end of this period, the 40 subjects are randomlydivided into two groups of 20.

The “test” and “control” fabric pieces are then tacked into 40 cleancotton or polyester cotton shirts in the underarm region in such amanner that in 20 shirts, the control fabric pieces are attached insidethe left underarm region, and the test fabric pieces are attached in theright underarm region. For the remaining 20 shirts, the placing ofcontrol and test pieces of fabric is reversed.

The shirts carrying the tacked-in fabric inserts are then worn by the 40panel members for a period of 5 hours, during which time each panellistperforms his normal work function without unnecessary exercise.

After this five hour period, the shirts are removed and the insertsdetached and placed in polyethylene pouches prior to assessment by thetrained panel of assessors.

The malodour intensity of each fabric insert is evaluated by all threeassessors who, operating without knowledge of which inserts are “test”and in which are “control” and, without knowing the scores assigned bytheir fellow assessors, sniff each fabric piece and assign to it a scorecorresponding to the is strength of the odour on a scale from 0 to 5,with 0 representing no odour and 5 representing very strong odour.

Standard aqueous solutions of isovaleric acid which correspond to eachof the scores 1, 2, 3, 4 and 5 are provided for reference to assist theassessors in the malodour evaluation. These are shown below:

CONCENTRATION OF AQUEOUS SCORE ODOUR LEVEL ISOVALERIC ACID (ML/L) 0 NOODOUR 0 1 SLIGHT 0.013 2 DEFINITE 0.053 3 MODERATE 0.22 4 STRONG 0.87 5VERY STRONG 3.57

The scores recorded by each assessor for each fabric piece are averaged.The average score of the “test” fabric pieces is deducted from theaverage score of the “untreated” control fabric pieces to give aMalodour Reduction Value.

As a check that the selection of panel subjects is satisfactory foroperation of the test, the average score with unperfumed fabric piecesshould be between 2.5 and 3.0.

Preferred deodorant perfumes are those which have a Malodour ReductionValue of at least 0.50, or 0.70, or 1.00. The higher the minimum value,the more effective is the perfume as a deodorant as recorded by theassessors in the Malodour Reduction Value Test. It has also been notedthat consumers, who are not trained assessors, can detect byself-assessment a noticeable reduction in malodour on soiled fabric suchas shirts and underclothes where the Malodour Reduction Value is atleast 0.30, so the higher the Malodour Reduction Value above thisfigure, the more noticeable is the deodorant effect.

Selection of a combination of fragrance materials to give a deodoranteffect is explained in patents such as U.S. Pat. No. 4,306,79 referredto earlier. Further systems of selection are given in U.S. Pat. No.5,482,635 and U.S. Pat. No. 5,554,588 also mentioned above.

Such selections can be carried out using materials with preferred valuesof partition coefficient and Kovats index as discussed above.

U.S. Pat. No. 5,501,805 describes perfume compositions made from acombination of fragrance materials, where the composition is a deodorantperfume yet has a relatively low odour. Such “low-odour” deodorantperfumes may be used in the present invention.

When this test is used to assess the deodorant effectiveness of aperfume composition, applied to fabric in accordance with thisinvention, the test fabric is a blend of 95% by weight cotton and 5% byweight spandex fibres. The control fabric is 100% cotton. The test andcontrol fibres are selected to be similar in other respects, inparticular to have the same weight per unit area.

The test fabric is subjected to treatment with a fabric finishingliquor, containing perfume, so as to apply 0.5% of the perfume, byweight of the fabric. The control fabric is treated similarly, butwithout perfume.

The test and control fabrics are not subsequently washed before testing.

However, this test procedure can be operated in other ways. Todemonstrate the higher deposition of perfume on spandex fibres, thecontrol and test fabrics are both treated with the same fabric finishingliquor containing perfume. To isolate the deodorant effect of theperfume, the test and control fabrics can be the same, but no perfume ispresent in the liquor used to treat the control fabric.

EXAMPLE 1

This model experiment demonstrates perfume deposition on spandex fibres.A mixture of perfume ingredients was prepared and added to anunperfumed, but otherwise conventional, laundry detergent powder, toprovide a perfume concentration of 0.5% by weight.

The perfumed powder was used to wash test cloths which had notpreviously been treated with any perfume. These were either all cotton,or 95% cotton with 5% spandex. After washing, the cloths were rinsed andthen line dried overnight.

The perfume was extracted from the dry cloths with organic solvent, andthe content of the perfume ingredients in the solvent extracts wasdetermined by gas chromatography. If the concentration of an ingredientextracted from the spandex-containing cloth was greater than from theall-cotton cloth by a factor of 5 to 20, the result was coded as amedium enhancement (M). If the concentration was greater by 20 or more,it was coded high(H) and if less than 5 or not measurable, it wascoded(L). The results obtained were as follows:

Ingredient K* logP** Enhancement Category Boisambrene Forte 1714 5.5 M Bbenzyl acetone 1206 2.0 M — citronellol 1209 3.6 H A′ 2,6-dimethyl- 9752.9 L — heptan-2-ol jasmacyclene 1394 2.9 H B′ methyl salicylate 11672.3 L — 2-phenylethanol 1087 1.4 L — terpinyl acetate 1331 4.0 H B′tetrahydrogeraniol 1180 3.6 H A′ tetrahydrolinalol 1083 3.5 H A′ Tonalid1840 6.4 M B yara 1416 3.2 H B′ *Measured on OV-1 polydimethylsiloxane(Ohio Valley) as stationary phase using capiliary gc **Measured orestimated using ‘logP’ software from ACD Inc.

EXAMPLE 2

Cloth composed of 90% cotton, 10% spandex, was treated in a fabricfinishing step, using conventional equipment. Other cloth, consisting ofcotton only, was treated in the same way. In both cases, the fabricfinishing treatment was carried out for a period of 20 minutes, using anMCS jet machine (Urgano, Italy). The finishing liquors were appliedapplied at a liquor to cloth ratio of 20:1, at 40° C. with a pH of 5.5.These liquors all contained Ceranine HCS (a finishing agent made bySandoz) at a concentration such that this agent was applied to fabric at1% by weight of the fabric.

The treatment liquors also contained perfume at varying concentrations,so that this was applied to the fabric at concentrations of 0.01%, 0.1%and 1% by weight of the fabric. Liquor without perfume was used toprovide a control.

The perfume was used, designated “perfume U” contained 33.5% (by weightof the perfume composition) of fragrance materials in category A above,all of which had Kovats indices of 1050 to 1600 and therefore all fellwithin category A′. The perfume also contained 41.1% (by weight of theperfume composition) of materials in category B. These were made up from26.7% with Kovats index over 1600 and 14.4% with Kovats index of 1300 to1600, so as to fall within category B′.

The cloths were then washed repeatedly, using a commercial detergentpowder which included a different perfume. The washes were carried outusing a Miele washing machine on its “Quickwash” programme at 40° C. 110gm of detergent powder was used for each wash. The fabric was rinsedthree times after each wash and tumble dried.

The dried cloths were examined by a panel of in expert assessors ofperfume intensity. This was to determine the intensity of perfume on thefabric, but not its deodorant property. The results obtained were asfollows:

Odour Evaluation Scores 90% cotton and 10% 100 cotton spandex Washes: 13 5 1 3 5 Perfume U   0% 2.0 2.4 2.8 4.0 4.4 4.6 1.0% 6.4 3.6 <3 16.014.0 12.8 0.1% 3.6 <3 <3 10.4 9.7 9.0 0.01%  3.2 <3 <3 8.8 8.0 7.2

It can be seen that the cloths which were not perfumed in the finishingtreatment took up perfume in the first wash and this perfume built upslowly in subsequent washes. The quantity of perfume taken up wasgreater on the cloth which included spandex fibres.

The cloths containing spandex fibres which were perfumed during thefinishing treatment had a much higher level of perfume on them after onewash than the 100% cotton cloths. Even after five washes, the intensityof perfume on them exceeded the intensity of perfume on the 100% cottoncloths after one wash, and on the cloths which had not been perfumedprior to the first wash. Thus the spandex fibres were providing enhancedretention of perfume as well as enhanced deposition.

The 100% cotton cloths which had been perfumed during the finishingtreatment were assessed again after 3 and 5 washes. The results showedthat the level of intensity of the perfume was less than that observedafter 1 wash but also showed that the olfactive differences betweenperfume U used in the finishing treatment and the perfume present in thewashing powder was confusing the panellists.

EXAMPLE 3

Two deodorant perfumes were used in treatment of cloths by a finishingprocess as in Example 2.

Perfume L contained materials in the above categories as follows:

Category A: 30 wt % (all with Kovats index above 1600)

Category B: 68.5 wt % (13% with Kovats index 1300-1600 and thereforewithin category B′, and 55.5 wt % with Kovats index above 1600).

Perfume M contained materials in the above categories as follows:

Category A: 24.9 wt % (16.3 wt % with Kovats index 1050-1600 andtherefore within category A′, and 8.6 wt % with Kovats index above 1600)

Category B: 55.3 wt % (8.6 wt % with Kovats index 1300-1600 andtherefore within category B′, and 46.7 wt % with Kovats index above1600).

The test cloths were: 100% cotton, 90% cotton with 10% spandex, 95%cotton with 5% spandex, 100% nylon and 82% nylon with 18% spandex.Perfume was used at a concentration of 0.5% based on the weight of thefabric. The treated cloths were tested for Malodour reduction in thetest described earlier. The control cloths were 100% cotton, which hadbeen subjected to the same finishing treatment, but without perfume inthat finishing treatment. The results are set out in the followingtables, which show substantial enhancements of malodour inhibition whenfabrics containing spandex fibres were used.

Test 1: perfume M (% by Malodour Fabric weight reduction other ofMalodour Maldour as % of fibre spandex fabric) score reduction control90% 10% 0.5% 1.19 1.46   55% cotton 100% 0 0.5% 1.92 0.73 27.4% cotton82% nylon 18% 0.5% 1.00 1.65 62.1% 100% 0 0.5% 1.97 0.68 25.5% nylon100% 0 0 2.65 cotton (control) Notes: % malodour reduction calculated as100% x(control score-sample score)/control score Statistical calculationshowed that a difference in malodour reduction of 6.9% was significantat 95% level of confidence.

Test 2: perfume M (% by Malodour Fabric weight reduction other ofMalodour Maldour as % of fibre spandex fabric) score reduction control95% 5% 0.5% L 1.15 1.22 51.5% cotton 95% 5% 0.5% M 1.29 1.08 45.6%cotton 100% 0 0 2.37 cotton (control) Note: Statistical calculationshowed that a difference in malodour reduction of 6.3% was significantat 95% level of confidence.

In test 1, malodour scores on 100% cotton fabric, with and withoutperfume, demonstrate a malodour reduction value of 0.73 attributable tothe perfume. A similar malodour reduction value was observed when thetest cloth was 100% nylon.

When spandex fibre was incorporated, the malodour reduction increasedgreatly, showing that increased deposition of perfume on spandex fibrescompared with other fibres also provides an increased deodorantefficiency.

In test 2, similar high values of malodour reduction were obtained wheneither perfume L or perfume M was used, in test fabrics with 5% byweight spandex fibres.

What is claimed is:
 1. A spandex fiber having fragrance materialsdeposited on the spandex fiber from a solution wherein the fragrancematerials are selected from: Category A) hydroxylic materials which arealcohols, phenols or salicylates, with an octanol/water partitioncoefficient (P) whose common logarithm (log10P) is 2.5 or greater, and agas chromatographic Kovats index (as determined on polydimethylsiloxaneas non-polar stationary phase) of at least 1050, and Category B) estersethers, nitrites, ketones or aldehydes, with an octanol/water partitioncoefficient (P) whose common logarithm (log10P) is 2.5 or greater, and agas chromatographic Kovats index (as determined on polydimethylsiloxaneas non-polar station phase) of at least
 1300. 2. A textile whichcomprises spandex and other fibers and which has fragrance materialspreferentially deposited on the spandex fibers from a solution whereinthe fragrance materials are selected from: Category A) hydroxylicmaterials which are alcohols, phenols or salicylates, with anoctanol/water partition coefficient (P) whose common logarithm (log10P)is 2.5 or greater, and a gas chromatographic Kovats index (as determinedon polydimethylsiloxane as non-polar stationary phase) of at least 1050,and Category B) esters ethers, nitrites, ketones or aldehydes, with anoctanol/water partition coefficient (P) whose common logarithm (log10P)is 2.5 or greater, and a gas chromatographic Kovats index (as determinedon polydimethylsiloxane as non-polar station phase) of at least
 1300. 3.A textile which is yarn or textile goods that have never been worn asgarments and that contain spandex, comprising contacting the textilewith a solution containing a perfume composition which is a mixture offragrance materials, so that fragrance materials are deposited on thetextile, wherein the perfume composition contains at least 50%, byweight of the perfume composition, of fragrance materials selected fromCategory A) hydroxylic materials which are alcohols, phenols orsalicylates, with an octanol/water partition coefficient (P) whosecommon logarithm (log₁₀P) is 2.5 or greater, and a gas chromatographicKovats index (as determined on polydimethylsiloxane as non-polarstationary phase) of at least 1050, and Category B) esters, ethers,nitriles, ketones or aldehydes, with an octanol/water partitioncoefficient (P) whose common logarithm (log₁₀P) is 2.5 or greater, and agas chromatographic Kovats index (as determined on polydimethylsiloxaneas non-polar stationary phase) of at least
 1300. 4. A textile accordingto claim 3 which contains from 0.5 to 50% spandex fibers and the amountof fragrance materials deposited thereon is from 0.001% to 1% by weightof the textile.
 5. A method of treating textile which is yarn or textilegoods that have never been worn as garments and that contain spandex,comprising contacting the textile with a solution containing a perfumecomposition which is a mixture of fragrance materials, so that fragrancematerials are deposited on the textile, wherein the perfume compositioncontains at least 50%, by weight of the perfume composition, offragrance materials selected from Category A) hydroxylic materials whichare alcohols, phenols or salicylates, with an octanol/water partitioncoefficient (P) whose common logarithm (log₁₀P) is 2.5 or greater, and agas chromatographic Kovats index (as determined on polydimethylsiloxaneas non-polar stationary phase) of at least 1050, and Category B) esters,ethers, nitrites, ketones or aldehydes, with an octanol/water partitioncoefficient (P) whose common logarithm (log₁₀P) is 2.5 or greater, and agas chromatographic Kovats index (as determined on polydimethylsiloxaneas non-polar stationary phase) of at least
 1300. 6. A method accordingto claim 5 wherein the textile contains from 0.5 wt % to 50 wt % spandexfibers and the amount of fragrance materials deposited on the textile isfrom 0.001% to 1% by weight of the textile.
 7. A method of treating aspandex fiber comprising contacting the fiber with a solution containinga perfume composition which is a mixture of fragrance materials, so thatfragrance materials are deposited on the spandex fiber, wherein theperfume composition contains at least 50%, by weight of the perfumecomposition, of fragrance materials selected from Category A) hydroxylicmaterials which are alcohols, phenols or salicylates, with anoctanol/water partition coefficient (P) whose common logarithm (log₁₀P)is 2.5 or greater, and a gas chromatographic Kovats index (as determinedon polydimethylsiloxane as non-polar stationary phase) of at least 1050,and Category B) esters, ethers, nitriles, ketones or aldehydes, with anoctanol/water partition coefficient (P) whose common logarithm (log₁₀P)is 2.5 or greater, and a gas chromatographic Kovats index (as determinedon polydimethylsiloxane as non-polar stationary phase) of at least 1300.8. A method according to claim 5 or claim 7 wherein the perfumecomposition contains at least 10%, by weight of the perfume composition,of fragrance materials selected from: Category A′) hydroxylic materialswhich are alcohols, phenols or salicylates, with an octanol/waterpartition coefficient (P) whose common logarithm (log₁₀P) is 2.5 orgreater, and a gas chromatographic Kovats index (as determined onpolydimethylsiloxane as non-polar stationary phase) lying within therange 1050 to 1600, and Category B′) esters, ethers, nitriles, ketonesor aldehydes, with an octanol/water partition coefficient (P) whosecommon logarithm (log₁₀P) is 2.5 or greater, and a gas chromatographicKovats index (as determined on polydimethylsiloxane as non-polarstationary phase) lying within the range 1300 to
 1600. 9. A methodaccording to claim 5 or claim 7 wherein the perfume composition containsat least 70%, by weight of the perfume composition, of fragrancematerials that are selected from categories A and B, which materialsinclude at least 25% by weight of the perfume composition, of fragrancematerials from the categories A′ and B′ defined in claim
 8. 10. A methodaccording to claim 9 wherein the perfume composition contains at least80%, by weight of the perfume composition, of fragrance materialsselected from categories A and B, which materials include at least 40%,by weight of the perfume composition, from categories A′ and B′.
 11. Themethod of claim 5, wherein the fabric is contacted with the perfumecomposition in a fabric finishing step.